Leather polyurethane

Depending on fashion, each year different materials have been and are currently used in the manufacturing of shoes, ranging from rubber soles (vulcanized styrene-butadiene rubber (SBR), thermoplastic rubber, EPDM) to different polymers (leather, polyurethanes, ethylene-vinyl acetate (EVA) copolymers, polyvinyl chloride (PVC), polyethylene, Phylon). To produce adequate adhesive joints, surface preparation of those materials is required (see part B Surface treatments). Surface preparation procedures for these materials must be quickly developed and the validity of these treatments is generally too short. Several procedures have been established to optimize the upper to sole bonding, most of them are based in the use of organic solvents. Due to environmental and health issues, solvents should be removed from the surface preparation procedure and several environmental friendly procedures for the surface preparation of several materials have been proposed. 

In the second quarter of the twentieth century, with the development of poly(vinyl chloride), nylon, polyurethane, and other polymers, many new and improved leather-like materials, so-called coated fabrics (qv), were placed on the market. Shortages of leather after World War 11 led to the expansion of these leather-like materials ("man-made" leathers) to replace leather in shoes, clothing, bags, upholstery, and other items. DurabiUty and waterproof quahties superior to leather made coated fabrics advantageous, in spite of imperfection in breathabihty and flexibiUty. Demands for shoes, clothing, and other items are stiU increasing due to growing world population and urbanization. 

Water-Vapor Permeability. Water-vapor permeabiUty depends on the polymer used for the coating layer and its stmcture. Vinyl-coated fabrics have Httie water-vapor permeabiUty due to the coating layer. Although polyurethane polymer is water-vapor permeable, urethane-coated fabrics also have low permeabiUty values due to their soHd layer stmcture. On the other hand, man-made leathers have good permeabiUty values as high as that of leather due to their porous layer stmcture. The permeabiUty of grain-type is lower than that of suede-type, influenced by finishing method. 

Man-Made Leathers. These materials contain a nonwoven fabric which is impregnated with a polyurethane to improve fiexibiHty, processibiHty, and conformabiHty (Fig. 9). Advanced man-made leathers contain microfibers as fine as 0.03 tex (0.3 den) or less to imitate coUagen fiber bundles, thereby attaining the soft feel and appearance essential for soft leather use. Polyurethane in the substrate is usually provided with porous stmcture by poromeric technology. The coating layer is also porous in the two-layer type man-made leathers (5—10). 

The late 1950s saw the emergence of cast elastomers, which led to the development of reaction injection mol ding (RIM) at Bayer AG in Leverkusen, Germany, in 1964 (see Plastics processing). Also, thermoplastic polyurethane elastomers (TPUs) and Spandex fibers (see Fibers, elastomeric) were introduced during this time. In addition, urethane-based synthetic leather (see Leather-LIKEmaterials) was introduced by Du Pont under the trade name Corfam in 1963. 

Aqueous dispersions of polyurethanes have also become available which may be used instead of solutions in organic solvents for such applications as leather treatment, adhesives and surface coatings. 

Since it possesses good properties of both PVC plastics and polyurethane elastomers, it has been used in those areas where PVC and polyurethane have traditionally played dominant roles. For example, it is a very promising replacement for flexible PVC used for medical purposes and in the food industry [I6,l7], because it essentially eliminates the concern regarding plasticizer contamination. It has been used in combination with the copolymer of butadiene and acrylonitrile (NBR) to make the abrasion-resistant aprons and rolls used on textile machines [18]. A PVC/TPU/ABS blend serves as a substitute for leather [19]. This could have a tremendous impact on the shoe industry. It has also been found to have an application as a building coating [20,21]. This trend will certainly grow and more applications will be found. This in turn should bring new developments in the material itself. 

Peel Strength Values of Vulcanized Styrene-Butadiene Rubber (SBR) Rubber/Polyurethane Adhesive/Leather Joints... 

FIGURE 27.9 T-peel strength values of styrene-butadiene rubber (SBS) treated with chloramine T aqueous solutions with different pH/waterbome polyurethane adhesive/roughened leather joints, as a function of the pH value of the chloramine T aqueous solutions. A adhesion failure to the rubber, M cohesive failure in tbe rubber. (From Navarro-Banon, M.V., Pastor-Bias, M.M., and Martm-Martinez, J.M., Proceedings of the 27th Adhesion Society, Wilmington, NC.)... 

Polyurethane adhesives are used for bonding wood, plastics, metals and leather. They can bond rubber to rubber, metal, glass or synthetic fibres. 

Caprolactam is used primarily in the manufacture of synthetic fibres and resins (especially nylon 6), bristles, film, coatings synthetic leather, plasticizers and paint vehicles as a cross-linking agent for polyurethanes and in the synthesis of the amino acid lysine (Lewis, 1993). 

Caprolactone is claimed as a component in one-paste-type resin compositions for denture bases <2002JPP2002104912> and e-caprolactone copolymers are suggested as components in polyurethane-based multilayered artificial leather sheets <2004JPP2004250808, 2004JPP2004250809>. 

The polyurethane (PU) can be considered an environment-friendly material because the urethane bond resembles the amide bond, which implies possible biodegradability. It can be used in various elastomer formulations, paints, adhesives for polymers and glass, and artificial leather as well as in biomedical and cosmetic fields. Polyurethane spheres were prepared from 20/40% of PU prepolymer solution in xylene [91]. PU droplets were formed in water with the SPG membrane of different pore size (1.5-9.5 pm) and then polymerized to form the final microspheres. Finally, spherical and solid PU particles of 5 pm were obtained after the removal of the solvent. In another study, Ma et al. reported the formation of uniform polyurethane-vinylpolymer (PUU-VP) hybrid microspheres of about 20 pm, prepared using SPG membranes and a subsequent radical suspension polymerization process [92], The prepolymers were solubilized in xylene and pressed through the SPG membrane into the continuous phase containing a stabilizer to form uniform droplets. The droplets were left for chain extension at room temperature for some hours with di- and triamines by suspension polymerization at 70 °C for 24h. Solid and spherical PU-VP hybrid particles with a smooth surface and a higher destructive strength were obtained. 

Surface treatment of textiles, leather, glass, wood, and paper is the second largest application for fluorinated polyurethanes. The coatings are applied in one-step treatment and impart resistance to soil, water, oil, and stains as well as a smoothness to fabrics and leather that resists removal by many cycles of laundering or dry cleaning.52... 

We soon realized that the photodecoration of leather was a big challenge. The tanning process introduced a large number of chemicals into hides, which already contained many reactive species, including phenolic substances that could interact with our chemistry. We thus had to learn to put blocking layers onto the hides and, subsequently, embed our chemistry in polyurethane binders, which would provide the required flexibility to these coatings. After imaging, a fix layer, which would contain phenolic radical traps and UV absorbers, was applied. 

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